Blends of polyolefins and poly amides

ABSTRACT

A NEW CLASS OF BASIC POLYAMIDES HAVING A MOLECULAR WEIGHT BETWEEN ABOUT 2,000 AND 200,000. THE POLYAMIDES ARE PREPARED BY FIRST REACTING AN ACRYLIC OR METHACRYLIC ESTER WITH A MONOAMINE AND THEN FURTHER REACTING THE PRODUCT OBTAINABLE WITH A POLYAMIDE. THE POLYAMIDES ARE SUITABLE FOR USE AS TINCTORIAL MODIFIERS FOR POLYMERIC MATERIALS AND PARTICULARLY FOR CRYSTALLINE POLYOLEFINS CONSISTING ESSENTIALLY OF ISOTACTIC MACROMOLECULES.

United States Patent Matter enclosed in heavy brackets appears in theoriginal patent but forms no part of this reissue specification; matterprinted in italics indicates the additions made by reissue.

ABSTRACT OF THE DISCLOSURE A new class of basic polyamides having amolecular weight between about 2,000 and 200,000. The polyamides areprepared by first reacting an acrylic or methacrylic ester with amonoamine and then further reacting the product obtainable with apolyamine. The polyamides are suitable for use as tinctorial modifiersfor polymeric materials and particularly for crystalline polyolefinsconsisting essentially of isotactic macromolecules.

CROSS-REFERENCES T O RELA TED APPLICATIONS This is an application forreissue of Letters Patent No. 3,668,278, issued on June 6, 1972, toAlberto Bonvicini and Giuseppe Camatore.

BACKGROUND OF THE INVENTION 1. Field of the Invention This inventionpertains to the field of tinctorial modifiers for polymeric materials.More particularly, this invention concerns the tinctorial modificationof polymeric materials with basic polyamides.

2. Description of the Prior Art Increasing the receptivity to dyes ofarticles manufactured from polyolefins consisting essentially ofisotactic macromolecules, by mixing the polymers, before forming, withcondensation resins characterized by the functional group NHCO- isknown.

Such resins, preferably having a low degree of condensation, areobtained from the polycondensation of higher amino acids, from thecondensation of diamines with bicarboxylic acids, from the condensationof cyclic amides such as the e-caprolactam (polyamides), or from thereaction of di-isocyanates with higher glycols (polyurethanes) and fromthe reaction of di-isocyanates with diamines (polyureas).

Similarly, the tinctorial modification of polypropylene by the additionof basic polyamides obtained by (l) the polycondensation ofisocinchromeronic acid with diamines as described in Italian Pat. No.692,162, (2) the polycondensation of N,N'-bis(w-carboalkoxyalkyl)piperazine with a diamine as described in Italian Pat. No. 7 85,- 574,and (3) the reaction of an acrylic or methacrylic ester with one or morepolyamines, is known.

Also, in a series of articles in Chimica e Industria" (March 1967, p.271; May 1967, p. 453; June 1967, p. 5 87; August 1967, p. 826), anumber of basic polyamides obtained by polycondensation of variousdiacrylyl derivatives with different amines have been described.

SUMMARY OF THE INVENTION We have discovered a new class of basicpolyamides and an economical process for preparation thereof. The

Re. 28,167 Reissued Sept. 17, 1974 ice polyamides of the presentinvention are suitable for use as tinctorial modifiers for polymers,particularly olefinic polymers. Thus, incorporation of the polyamides ofthe present invention into such a polymer renders the polymerparticularly receptive to dyes of the acid, metallized and plastosolubleclasses.

Additionally, we have found that when the basic polyamides of thepresent invention are incorporated into crystalline polyolefinsconsisting essentially of isotactic macromolecules, the workability ofsuch mixes in the granulating, extrusion, stretching and textilefinishing operations is substantially improved.

The polyamides of the present invention may be prepared by reacting amonoamine with an ester of acrylic or methacrylic acid and furtherreacting the product thus obtained with a polyamine. Preferably, thepolyamides of the present invention have molecular weights in the rangeof from about 2,000 to 200,000.

The basic polyamides of the present invention have the formula:

I7 r l TI /TQ /TJI (I) R: l wherein:

n and m are integers from 1 to 99; b is an integer;

N is nitrogen; [R1 is wherein R is hydrogen, alkyl, aryl selected fromthe group consisting of the phenyl and naphthyl series, lowercycloalkyl, or R and the nitrogen to which it is bonded taken togetherform a heterocyclic ring; or R is COOR, wherein R is lower alkylcontaining one to eight carbon atoms;] R: is an aliphatic radical,cycloaliphatic radical, or aromatic radical selected from the groupconsisting of the phenyl and naphthyl series, which radical contains upto 30 carbon atoms; A is wherein R is hydrogen or lower alkyl;

wherein R is hydrogen or lower alkyl,

R7 is methylene,

arylene selected from the group consisting of the phenylene series, orlower alkylenearylene wherein the arylene portion is selected from thegroup consisting of the phenylene series, and a is an integer from 1 to10; with the proviso that when a is l,

R may also be (1) R -NHR,,-

wherein R may be the same or different and is lower alkylene or +R -NHRwherein R is CH,, or -C H and z is an integer from 1 to 5, or R may alsobe (2) a heterocyclic bivalent residue which may contain heteroatomsselected from the group consisting of nitrogen in the form of secondaryor tertiary amine group, oxygen, sulfur, and phosphorus; or

R is as defined hereinabove Rm is 01' C2H4, and y is 0 or 1,

and wherein R R ,A, X and b are such that the molecular weight of thepolyamide is between about 2,000 and 200,000.

While, as would be appreciated in this art, many different terminalgroups could be introduced onto the polyamides of the present inventionwithout substantially affecting the nature thereof or departing fromthis invention, and while it is the usual practice in the art to omitterminal groups from a description of long chain polymers, particularlysince such groups are generally not detectable by routine analysis,nevertheless, for completeness, it will be understood that, as producedat the end 0 the condensation reaction, the polyamides can generally berepresented as being terminated by terminals R which may be the same ordiflerent, as in the following formula:

l ns, wherein: n, m, b, N, R A and X are as defined above and R is -NHRwherein R is hydrogen, an alkyl radical, an aryl radical selected fromthe group consisting of radicals of the phenyl and naphthyl series, orcycloalkyl radical or R and the nitrogen to which it is bonded, takentogether, form a heterocyclic ring, or R is COOR wherein R is a loweralkyl radical containing 1 to 8 carbon atoms.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferably, the portion offormula I designated:

is a residue of a monoamine selected from the group consisting ofmethylamine, ethylamine, propylamine, butylamine, hexylamine,octylamine, dodecylamine, octadecylamine, cyclohexylamine, aniline, andp-toluidine.

Preferably, the portion of formula I designated:

is a residue of methylacrylate, [ethylarcylate] ethylacrylate,methylmethacrylate, butylacrylate, butylmethacrylate or2-ethylhexylacrylate.

Preferably, the portion of formula I designated:

is a residue of a polyamine having the formula wherein R R R a and y areas defined hereinabove. Most preferably, the portion of formula Idesignated:

is a residue of a polyamine selected from the group consisting ofethylenediamine, hexamethylenediamine, diethylenetriarnine,tetraethylenepentamine, piperazine, N-(Z- aminoethyl)piperazine,p-phenylcnediamine, 4,4'-methylenedianiline,N,N-dimethylhexamethylenediamine and N,N-dibutylhexamethylenediamine.

The polyamides of the present invention may be easily and cheaplyobtained by reacting an acrylic or methacrylic ester with aliphatic,cycloaliphatic or aromatic monoamines containing up to 30 carbons, suchas, for instance: methylamine, ethylamine, propylamine, butylamine,hexylamine, octylamine, dodecylamine, octadecylamine, cyclohexylamine,aniline, and p-toluidine, and then reacting the product of that reactionwith one or more polyamines.

lPreferable acrylic esters are those with a low number of carbon atoms,such as: methylacrylate, ethylacrylate, and methylmethacrylate. However,acrylic esters with a greater number of carbon atoms such as, forexample, butylacrylate, butylmethacrylate, 2 ethylhexylacrylatc, andother like acrylic esters, may be used.

Preferably, the polyamine has the formula a N'Rio-I \l /y wherein R R Ra and y are as defined hereinabove.

Most preferably, the polyamine is selected from the group consisting ofethylenediamine, hexamethylenediamine, diethylenetriamine,tetraethylenepentamine, piperazine, N-(Z-aminoethyl)piperazine,p-phenylenediamine, 4,4 methylenedianiline, N,N'dimethylhexamethylenediamine and N,N-dibutylhexamethylenediamine.

The basic polyamides may be prepared in the presence or absence ofsolvents and/ or condensing agents, by first reacting the acrylic ormethacrylic ester with the aliphatic or aromatic monoamine containing upto 30 carbon atoms. The reaction product is then reacted with thepolyamine by simply adding the polyamine to the reaction mixture. Bothof the reactants, i.e., that of the acrylate with the monoamine and thatof product thereof with the polyamine, may be carried out attemperatures ranging from room temperature to about C.

The polycondensation is completed by heating at temperatures in therange between about 120 and 300 C. Also, a vacuum may be used in orderto remove from the reaction system the alcohol that is released by thepolycondensation.

The molar ratio between the acrylic ester or the methacrylic ester andthe total amines is preferably 1:1. However, an excess of one or theother of the reactants may also be used. Preferably an excess of thetotal amines up to 30 percent is used.

The aliphatic, cycloaliphatic or aromatic monoamine containing up to 30carbon atoms and the polyamine (or the mixture of several amines) may bepresent in the reaction mixture in a wide ratio to each other. Withrespect to the total amines, each amine, i.e., the monoarnine and thepolyamine, may, in fact, vary from 1-99 percent moles.

If desired, additional acrylate or monoamine may be added along with thepolyamine.

Additionally, we have found that, when the polymer is a crystallinepolyolefin consisting of isotactic macromolecules, the workability ofthe miX (i.e., with the polyamide of the present invention) is improvedwhen the polyolefin is present in an amount from about 99-75 percent andpreferably 98-90 percent by weight of the total mix and the poly-amideis present in an amount from about 1-25 percent and preferably 2-10percent by weight of the total mix.

Suitable for use with the polyamides of the present are, in general,crystalline polyolefins obtained from monomers of the formula RCH=CHwherein R is an alkyl or aryl group, or a hydrogen atom, and preferablyis lower alkyl or an aryl group of the phenyl series. Particularlypreferred are polyethylene, polypropylene, polybutene-l,poly-4-methylpentene-1, polystyrene and the like.

The polyamides of the present invention are also suitable tinctorialmodifiers for fibrogenous polymers of a type other than olefinicpolymers, such as, for example, acrylic polymers, e.g.,polyacrylonitrile, vinyl polymers, e.g., polyvinyl chloride, polyesters,polyamides and the like.

Particularly suitable are those polyolefins consisting mainly ofisotactic macromolecules obtained by low-pressure polymerization withstereospecific catalysts.

Preferably, the crystalline polyolefin used is polypropylene consistingessentially of isotactic macromolecules, obtained by the stereospecificpolymerization of propylene, or a crystalline propylene-ethylenecopolymer with a predominant propylene content.

The mixing of the basic polyamide with the polyolefin, according to thisinvention, is generally carried out by simple mixing together of the twomaterials in the form of powders.

It is possible, however, to carry out the addition with other methods,such as, for instance, the mixing of the olefinic polymer with asolution of the basic polyamide in a suitable solvent, followed byevaporation of the solvent itself or by adding the basic polyamideduring or at the end of the polymerization. Additionally, it is alsopossible to directly mix the non-polycondensed reaction product of thereactants used for preparing the polyamide, with the polyolefin, byletting the polycondensation take place dur ing the thermal treatmentsto which the polymer is subjected during the granulation and spinningoperations.

The polyolefins may be in any form, depending on the desired end use,for example, films, strips, fibers and other formed objects.

When the polyolefin is to be in the form of a fiber, the mixes are firstgranulated and then extruded through suitable melt-spinning devices,operating in the absence of oxygen, but preferably in an atmosphere ofinert gases (e.g., nitrogen).

During the mixing, additives, as is well known to the art, such asdulling agents, pigments, organic or inorganic dyestuffs, stabilizers,lubricants, dispersants and the like, may be blended in.

The yarns, after spinning, may be subjected to a stretching or drawingprocess with a stretch ratio of from about 1:2 to 1:20, at temperaturesbetween about 80 and 150 C., in a stretching apparatus heated by hot airor by steam or a similar fluid, or fitted with heating plates.Alternatively, the fibers may be subjected to a strong orientation afterextrusion by methods well known in the art for such purposes.

It is also preferable to subject the yarns to a sizing treatment (sizestabilization) under free or impeded shrinkage, at about 80-1 60 C.,such sizing treatments being well known in the art.

The spinning may be carried out using conventional spinnerets,preferably spinnerets having holes with a diameter greater than about0.5 millimeter and with a length/ diameter ratio greater than about 1.1,but preferably between about and 30. The holes of the spinnerets mayhave either circular or non-circular cross sections.

The dyeable compositions, according to this invention, also may be usedin bicomponent fibers, e.g., either the inside or the outside lining ofsheath-core fibers or in sideby-side fibers, or as a part of aconjugated fiber, e.g., a eo-spun fiber. The yarns obtained may beeither monoor multi-filament and can be used for the preparation ofeither continuous filaments or staples, for the preparation of yarns orbulk staples, or for the preparation of nonwoven structures, i.e., spunbonded and non Wovens."

The monoor multi-filament fibers obtained according to this invention,if desired, may be subjected to further treatments with reactantscapable of rendering the basic polyamides completely insoluble in water.Particularly suitable reactants for this purpose are monoand diepoxides,monoand di-isocyanates, monoand di-aldehydes, halogens, divinylbenzeneand the like.

The fibers and other manufactured products may also be subjected to anacid treatment which will improve the dyeability and color fastness.These treatments can be carried out either before or after thestretching operation.

The fibers obtained according to this invention possess excellentreceptivity towards the dyes belonging to the classes of acid,metallized and plastosoluble dyes, and fibers thus dyed possess a goodstability and particularly good light fastness.

The following examples further illustrate our invention.

In the examples, the dyeing operations were carried out for 1 hours atthe boiling point, in dyeing baths containing 2.5 percent of dye (acid,pre-metallized or plastosoluble) based on the weight of the fibers, witha fiber/ bath ratio of 1:40.

The dyeings with acid and pre-metallized dyes were conducted in thepresence of 1 percent by weight, based on the weight of the fiber, of asurfactant consisting of the product of condensation of ethylene oxidewith an alkylphenol or of the sodium salt of N-oleyl-N-methyltaurine. 30minutes after the start of the boiling, 2 percent, based on the weightof the fiber, of a 20 percent solution of acetic acid was added in orderto improve the exhaustion of the baths.

The dyeings with plastosoluble dyes were conducted in the presence of 2percent of surfactant and 3 percent of ammonium acetate, based on theweight of the fiber.

After the dyeing, the yarns were rinsed with running water. The rinsedyarns appeared intensely dyed, both with the acid and the premetallizeddyes as well as with the plastosoluble dyes.

The light fastness, resistance to washing and rubbing of the dyedmaterial proved fully satisfactory.

EXAMPLE 1 269 g. (1 mole) of octadecylamine and 172 g. (2 moles) ofmethylacrylate were heated with stirring, under a nitrogen atmosphere,at a temperature of C. for 2 hours. To this mixture were then added 129g. (1 mole) of N- (Z-aminoethyl)-piperazine and the whole was thenfurther heated at 100 C. for 2 hours, at C. for 2 hours, at C. for 1hour and at C. for 1 hour, removing the methanol formed during thereaction. The reaction mixture was further treated for 1 hour at 180 C.under vacuum.

The product obtained was a solid, basic polyamide having a yellowishcolor, an inherent [intrinsic] viscosity (1;) of 0.08 dl./g., measuredin a 0.5 percent isopropanol solution, a melting point of 120 C., andtitratable nitrogen of 5.4 percent (calculated=5.5 percent).

EXAMPLE 2 g. 1 mole) of dodecylamine and 172 g. (2 moles) of methylacrylate were heated with stirring, under a nitrogen atmosphere, at 100C. for 2 hours. To this mixture were then added 129 g. (1 mole) ofN-(Z-aminoethyl)piperazine. The whole mixture was further heated at 100C. for 2 hours, at 120 C. for 2 hours, at 150 C. for 1 hour and at 180C. for 1 hour, removing all the methanol formed during the reaction. Thereaction mixture was further treated at 180 C. for 1 hour, under vacuum.

The basic polyamide thus obtained was a semi-solid product having alight yellow color, with a titratable nitrogen of 6.5 percent(calculated=6.6 percent).

7 EXAMPLE 3 269 g. (1 mole) of octadecylamine and 172 g. (2 moles) ofmethyl acrylate were heated with stirring, in a nitrogen current, at 100C. for 2 hours. To this mixture were then added 208 g. (1.1 moles) oftetraethylenepentamine, and the whole was heated at 100 C. for 2 hours,at 120 C. for 2 hours, at 150 C. for 1 hour and at 180 C. for 1 hour,removing the methanol that had formed during the reaction. The reactionmixture was further treated for 1 hour under vacuum at 180 C.

The basic polyamide thus obtained was a yellow solid having a titratablenitrogen of 10.0 percent (calculated =10.0 percent).

EXAMPLE 4 80.7 g. (0.3 moles) of octadecylamine and 51.6 g. (0.6 moles)of methyl acrylate were heated with stirring, in a nitrogen current, at100 C. for 2 hours. To this mixture were then added 129 g. (1 mole) ofN-(Z-aminoethyl) piperazine and 60.2 g. (0.7 mole) of methyl acrylate.The whole was then heated at 100 C. for 2 hours, at 120 C. for 2 hours,at 150 C. for 1 hour and at 180 C. for 1 hour, removing the methanolthat had formed during the reaction. The reaction mixture was furthertreated for 1 hour at 180 C. under vacuum.

The basic polyamide thus obtained was a light yellow solid, having aninherent [intrinsic] viscosity (1 of 0.08 dL/g. (measured in a 0.5percent isopropanol solution) and a titratable nitrogen of 9.85 percent(calculated=10.0 percent).

EXAMPLE 5 55.5 g. (0.3 mole) of dodecylamine and 51.6 g. (0.6 mole) ofmethyl acrylate were heated with stirring, in a nitrogen current, at 100C. for 2 hours. To this mixture were then added 129 g. (1 mole) ofN-(Z-aminoethyl) piperazine and 60.2 g. (0.7 mole) of methyl acrylate.The whole was then heated at 100 C. for 2 hours, 120 C. for 2 hours, at150 C. for 1 hour and at 180 C. for 1 hour, removing the methanol thathad formed during the reaction. The reaction mixture was further treatedfor 1 hour at 180 C. under vacuum.

The basic polyamide thus obtained was a waxy solid product having alight yellow color, an inherent [intrinsic] viscosity (1;) of 0.08dl./g. (measured in a 0.5 percent isopropanol solution) and a titratablenitrogen of 10.90 percent (calculated:l1.0 percent).

EXAMPLE 6 80.7 g. (0.3 mole) of octadecylamine and 60 g. (0.6 mole) ofmethylmcthacrylate were heated with stirring in a nitrogen current for 2hours at 100 C. To this mixture were then added 129 g. (1 mole) ofN-(Z-aminoethyl)piperazine and 70 g. (0.7 mole) of methylmethacrylate.The whole was then heated for 2 hours at 100 C., for 2 hours at 120 C.,for 1 hour at 150 C. and for 1 hour at 180 C., removing all the methanolthat had formed during the reaction. The reaction mixture was furthertreated for 1 hour at 180 C. under vacuum.

The basic polyamide thus obtained was a light yellow solid having aninherent [intrinsic] viscosity (0;) of 0.06 dl./g. (measured in a 0.5percent isopropanol solution) the titratable nitrogen being 9.35 percent(calculated=9.4 percent).

EXAMPLE 7 80.7 g. (0.3 mole) of octadecylamine and 51.6 g. (0.6 mole) ofmethyl acrylate were heated with stirring in a nitrogen current for 2hours at 100 C. To this mixture were then added 64.5 g. (0.5 mole) ofN-(Z-aminoethyl)piperazine, 94.5 g. (0.5 mole) of tetraethylenepentamineand 60.2 g. (0.7 mole) of methyl acrylate, and the whole was thenfurther heated for 2 hours at 100 C., for 2 hours at 120 C., for 1 hourat 150 C., and for 1 hour at 180 C., removing all the methanol that hadformed during the reaction. The mixture was then treated for 1 hour at180 C. under vacuum.

The basic polyamide thus obtained was a light yellow solid having aninherent [intrinsic] viscosity (1;) of 0.10 dl./ g. (measured on asolution of 0.5 percent in isopropanol) and a titratable nitrogen of12.2 percent (cal-. cu1ated=l2.2 percent).

EXAMPLE 8 80.7 g. (0.3 mole) of octadecylarnine and 51.6 g. (0.6 mole)of methyl acrylate were heated with stirring in a current of nitrogenfor 2 hours at C. To this mixture were then added 60 g. (1 mole) ofethylenediamine and 60.2 g. (0.7 mole) of methyl acrylate, and the wholewas then heated for 2 hours at 100 C., for 2 hours at C., for 1 hour atC. and for 1 hour at C., removing the methanol that had formed duringthe reaction. The mixture was then further treated for 1 hour at 180 C.under vacuum.

The basic polyamide thus obtained was a light yellow solid having aninherent [intrinsic] viscosity (1,) of 0.06 dl./ g. (measured in a 0.5percent isopropanol solution), the titratable nitrogen being 8.4 percent(calculated=8.6 percent).

EXAMPLE 9 53.8 g. (0.2 mole) of octadecylamine and 34.4 g. (0.4 mole) ofmethyl acrylate were heated with stirring in a current of nitrogen for 2hours at 100 C. To this mixture were then added 129 g. (1 mole) ofN-(Z-aminoethyl)piperazine and 68.8 g. (0.8 mole) of methyl acrylate,and the whole was then heated for 2 hours at 100 C., for 2 hours at 120C., for 1 hour at 150 C. and for 1 hour at 180 C., removing the methanolthat had formed during the reaction. The mixture was further treated for1 hour at 180 C. under vacuum.

The basic polyamide thus obtained was a light yellow solid producthaving an inherent [intrinsic] viscosity (1;) of 0.11 dl./g. (measuredin a 0.5 percent isopropanol solution), the titratable nitrogen being11.2 percent (calculated=11.3 percent).

EXAMPLE 10 80 g. of a basic polyamide, obtained as described in Example1, were mixed together with 920 g. of crystalline polypropyleneconsisting essentially of isotactic macromolecules (having a melt indexof 22.5, an ash content of 0.009 percent and a residue after heptaneextraction of 97.2 percent).

This mixture was then extruded at 220 C., and the granulate obtained wastransformed into fibers under the following conditions:

The fibers obtained possessed a good affinity towards the followingdyestuffs:

Red for Wool B (C.I. acid red 115). Alizarine Blue SE (C.I. acid blue43). Lanasyn Red 2GL (C.I. acid red 216).

Lanasyn Brown 3RL (C.I. acid brown 30).

The dyed fibers possessed good light fastness and good tastness towashing and rubbing.

EXAMPLE l1 70 g. of basic polyamide, obtained according to Example 2,were mixed together with 930 g. of crystalline polypropylene consistingessentially of isotactic macromolecules having a melt index of 22.5, anash content of 0.009 percent and a residue after heptane extraction of97.2 percent.

The mixture was extruded at 220 C., and the granulate obtained wastransformed into fibers under the following conditions:

Spinning:

Temperature of worm screw 235 C. Temperature of e x tr u din g head 240C. Temperature of spinneret 240 C. Spinneret 60 holes, each having adiameter of 0.8 mm. and a length of 16 mm. Winding speed 400 m./min.Stretching:

Temperature 130 C. Medium Steam. Stretching ratio 1:5.

The fibers obtained possessed a good afi'inity towards the dyes listedin Example 10. The dyed fibers possessed good light fastness and goodresistance to washing and rubbing.

EXAMPLE 12 50 g. of basic polyamide, obtained according to Example 3,were mixed together with 950 g. of crystalline polypropylene consistingessentially of isotactie macromolecules having a melt index of 22.5, anash content of 0.009 percent and a residue after heptane extraction of97.2 percent.

The mixture was extruded at 220 C., and the granulate obtained wastransformed into fibers under the following conditions:

Spinning:

Temperature of worm screw- 240 C. Temperature of extruding head- 240 C.Temperature of spinneret 245 C. Spinneret 60 holes, each having adiameter of 0.8 mm. and a length of 16 mm. Maximum pressure 51 kg./sq.cm. Winding speed 400 m./min. Stretching:

Temperature 130 C. Medium Steam. Stretching ratio 1:5.

The fibers obtained possessed good affinity towards the dyes listed inExample 10. The dyed fibers possessed good light fastness and goodresistance to washing and rubbing.

EXAMPLE 13 50 g. of a basic polyamide, obtained by reacting 80.7 g.

(0.3 moles) of octadecylamine, 11.8 g. (1.3 moles) of methylacrylate and129 g. (1 mole of N-(2-aminoethyl)- piperazine, were mixed together with950 g. of crystalline polypropylene consisting essentially of isotacticmacromolecules (melt index of 22.5, an ash content of 0.009 percent, andresidue after heptane extraction of 97.2 percent).

This mixture was extruded at 220 C., and the granulate obtained wastransformed into fibers under the following conditions:

The fibers obtained possessed a good afiinity towards the dyes listed inExample 10. The dyed fibers possessed good light fastness and goodresistance to washing and rubbing.

EXAMPLE 14 40 g. of a basic polyamide, obtained by reacting 55 .5 g.(0.3 moles) of dodecylamine, 111.8 g. 1.3 moles) of methylacrylate and129 g. (1 mole) of N-(2-aminoethyl)- piperazine, were mixed togetherwith 960 g. of crystalline polypropylene consisting essentially ofisotactic macromolecules (melt index of 22.5, an ash content of 0.009percent, and residue after heptane extraction of 97.2 percent).

The mixture was extruded at 220 C., and the granulate obtained wastransformed into fibers under the following conditions:

Spinning:

Temperature of worm screw 235 C. Temperature of extruding head- 235 C.Temperature of spinneret 240 C. Spinneret 60 holes, each having adiameter of 0.8 mm and a length of 16 mm.

Maximum pressure 52 kg./sq. cm.

Winding speed 400 m./min. Stretching:

Temperature 130 C.

Medium Steam.

Stretching ratio 1:5.

The fibers obtained possessed good affinity towards the dyes listed inExample 10. The fibers thus dyed possessed good light fastness and goodresistance to washing and rubbing.

EXAMPLE 15 50 g. of a basic polyamide, obtained by reacting 80.7 g. (0.3moles) of octadecylamine, 130 g. (1.3 moles) of methylmethacrylate and129 g. (1 mole) of N-(Z-aminoethyUpiperazine, were mixed together with950 g. of crystalline poplyproplene consisting essentially of isotacticmacromolecules having a melt index of 22.5, an ash content of 0.009percent and a residue after heptane extraction of 97.2 percent.

This mixture was extruded at 210 C., and the graduate obtained wastransformed into fibers under the following conditions:

Spinning:

Temperature of worm screw.. 230 C. Temperature of extruding head- 235 C.Temperature of spinneret 240 C. Spinneret 60 holes, each having adiameter of 0.8 mm. and a length of 16 mm. Maximum pressure 50 kg./sq.cm. Winding speed 400 m./min.

1 1 EXAMPLE Continued Stretching:

Temperature 130 C. Medium Steam. Stretching ratio 1:5.

The fibers thus obtained possessed good affinity towards the dyes listedin Example 10. The dyed fibers possessed good light fastness and goodresistance to washing and rubbing.

EXAMPLE 16 40 g. of a basic polyamide, obtained by reacting 80.7 g. (0.3moles) of octadecylamine, 111.8 g. (1.3 moles) of methylacrylate, 64.5g. (0.5 moles) of N-(2-aminoethyl)- piperazine and 94.5 g. (0.5 moles)of tetraethylenepentamine, were mixed together with 960 g. ofcrystalline polypropylene consisting essentially of isotacticmacromolecules having a melt index of 22.5, an ash content of 0.009percent and a residue after heptane extraction of 97.2 percent.

This mixture was extruded at 220 C., and the granulate obtained wastransformed into fibers under the following conditions:

Spinning:

Temperature of worm screw 240 C. Temperature of extruding head 240 C.Temperature of spinneret 245 C. Spinneret 60 holes, each having adiameter of 0.8 mm. and a length of 16 mm.

Maximum pressure 50 lcg./sq. cm.

Winding speed 400 m./min. Stretching:

Temperature 130 C.

Medium Steam.

Stretching ratio 1:5.

The fibers obtained possessed good aflinity towards the dyes listed inExample 10. The dye fibers possessed good light fastness and goodresistance to washing and rubbing.

EXAMPLE 17 50 g. of a basic polyamide, obtained by reacting 80.7 g. (0.3moles) of octadecylamine, 111.8 g. (1.3 moles) of methylacrylate and 60g. (1 mole) of ethylenediamine, were mixed together with 950 g. ofcrystalline polypropylene consisting essentially of isotacticmacromolecules having a meit index of 22.5, an ash content of 0.009percent, and a residue after heptane extraction of 97.2 percent.

This mixture was extruded at 220 C., and the granulate obtained wastransformed into fibers under the following conditions:

Spinning:

Temperature of worm screw 235 C, Temperature of extruding head 235 C.Temperature of spinneret 240 C. Spinneret 60 holes, each having adiameter of 0.8 mm. and a length of 16 mm. Maximum pressure 50 kg./sq.cm. Winding speed 400 m./min. Stretching:

Temperature 130" C. Medium Steam. Stretching ratio 1:5.

The fibers obtained possessed good aifinity towards the dyes listed inExample 10. The dyed fibers possessed good light fastness and goodresistance to washing and rubbing.

1 2 EXAMPLE 1s 40 g. of a basic polyamide, obtained by reacting 53.8 g.(0.2 moles) of octadecylamine, 103.2 g. (1.2 moles) of methylacrylateand 129 g. (1 mole) of N-(Z-aminoethyUpiperazine, were mixed togetherwith 960 g. of crystalline polypropylene consisting essentially ofisotactic macromolecules having a melt index of 22.5, an ash content of0.009 percent, and a residue after heptane extraction of 97.2 percent.

The mixture was extruded at 220 C., and the granulate obtained wastransformed into fibers under the following conditions:

Spinning:

Temperature of worm screw 235 C. Temperature of extruding head 240 C.Temperature of spinneret 245 C. Spinneret 60 holes, each having adiameter of 0.8 mm. and a length of 16 mm.

Maximum pressure 50 kg./sq. cm.

Winding speed 400 m./min. Stretching:

Temperature 130 C.

Medium Steam.

Stretching ratio 1:5.

The fibers obtained possessed good afi'inity towards the dyes listed inExample 10. The dyed fibers possessed good light fastness and goodresistance to washing and rubbing.

Variations can, of course, be made without departing from the spirit andscope of the invention.

Having thus described the invention, what is desired to be secured byLetters Patent and hereby claimed is:

We claim:

1. A dyeable polymeric composition comprising a blend of from about99-75 percent by weight of a crystalline polyolefin consistingessentially of isotactic macromolecules and from about 1-25 percent byweight of a basic polyamide, the monomeric units of which may be thesame or different, said polyamide having the formula:

n and m are integers from 1 to 99;

b is an integer;

N is nitrogen;

[R is NHR wherein R is hydrogen, an alkyl radical, an aryl radicalselected from the group consisting of radicals of the phenyl andnaphthyl series, or a lower cycloalkyl radical; or

R together with the nitrogen, form a heterocyclic ring;

R is COOR; wherein R is lower alkyl containing one to eight carbonatoms;]

R, is an aliphatic radical, a cycloaliphatic radical, or an aromaticradical selected from the group consisting of radicals of the phenyl andnaphthyl series, which radical contains up to 30 carbon atoms;

A is

wherein R may be the same or different and is a lower alkylene radical,or

wherein R is -CH,--- or C H and z is an integer from 1 to 5; or R may bea bivalent heterocyclic residue which may contain heteroatoms selectedfrom the group consisting of nitrogen in the form of secondary ortertiary amine groups, oxygen, sulfur and phosphorus; or

wherein R is as defined hereinabove, R is --CH;,-- or C H and y is 0 or1, the molecular weight of the polyamide being between about 2,000 and200,000.

2. The composition of claim 1, wherein the polyolefin is polyethylene,polypropylene, polybutene-l, poly-4- methylpentene-l, polystyrene or acrystalline ethylenepropylene copolymer having a predominant amount ofpropylene.

3. A dyeable composition comprising from about 99- 75 percent by weightof a crystalline polyolefin consisting essentially of isotacticmacromolecules, said polyolefin being selected from the group consistingof polyethylene, polypropylene, polybutene-l, poly-4-methylpentenel,polystyrene and a crystalline ethylene-propylene copolymer having apredominant amount of propylene, and from about l-25 percent by weightof the basic polyamide as defined in claim 1, wherein:

a. that portion of formula I designated:

iii

is a residue of a monoamine selected from the group consisting ofmethylamine, ethylamine, propylamine, butylamine, hexylamine,octylamine, dodecylamine, octadecylarnine, cyclohexylamine, aniline, andptoluidine;

b. that portion of formula I designated:

is a residue of methylacrylate, ethylacrylate, methylmethacrylate,butylacrylate, butylmethacrylate or 2- ethylhexylacrylate; and

c. that portion of formula I designated:

is a residue of a polyarnide selected from the group consisting ofethylenediamine, hexamethylenediamine, diethylenetriamine[diethylentriamine], tetraethylenepentamine, piperazine,N-(Z-aminoethyl) piperazine, [p-phenylenediamine,4,4'-methylenediamiline, N, N-] p-phenylenediamine,4,4'-melhylenedianiline, N,N-dimethylhexa methylenediamine andN,N-dibutylhexamethylenediamine.

4. The polymeric composition of claim 3, in the form of fibers, films,strips, or shaped articles.

5. The composition of claim I, wherein the basic polya-mide has terminalgroups of the formula R wherein R is NHR wherein R is hydr gen, an alkylradical, an aryl radical selected from the group consisting of radicalsof the phenyl and naphthyl series, or cycloalkyl radical or R and thenitrogen to which it is bonded, taken together, form a heterocyclicring, or R, is COOR wherein R is a lower alkyl radical c ntaining 1 to 8carbon atoms.

References Cited FOREIGN PATENTS 7/1961 Great Britain 260857 L 5/1961Canada 260857 L PAUL LIEBERMAN, Primary Examiner US. Cl. X.R.

l6ll73, 2602 R, 85.7, 857 UN, 857 PE. 857 TW, 860, 873, 898, 899, 901,78 A,

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. Re,28,167 Dated September 17. 1974 Inventor(s) Alberto BONVICINI andGiuseppe CANTATORE It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 1, line 9: "22,766/69" and "22,830/69" should read 22,766 A/69and 22,83 0 A/69 Column 3, line 10: "group," should read groups,

Column 4, line 48: "reactants, should read reactions,

Column 5, line 63: "80l 60"C." should read 80-l60 C.--

Column 9, line 43: "The" should read This Column 9, line 70: '(l mole"should read (1 mole) Column 10, line 63: "graduate" should readgranulate Column 14, line 15: "polyamide" should read polyamine Signedand sealed this 3rd day of December 1974.

(SEAL) Attest:

C. MARSHALL DANN McCOY M. GIBSON JR.

Commissioner of Patents Attesting Officer

